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Chapter 12

Refining of Stainless Steels


B.V. Patil, Manager, Process Research & Development, Allegheny Ludlum Corp.
A.H. Chan, Manager of AOD Process Technology, Praxair Inc.
R.J. Choulet, Consultant to Praxair, Inc.

12.1 Introduction
Stainless steels contain from 10 to 30% chromium. Varying amounts of nickel, molybdenum, copper, sulfur, titanium, niobium, etc. may be added to obtain desired mechanical properties and service life. Stainless steels are primarily classified as austenitic, ferritic, martensitic, duplex or
precipitation hardening grades. The first stainless steel grades that were commercially produced in
the United States were similar to 302, 410, 420, 430, and 446. These five alloys were produced
and marketed prior to 1930. In subsequent years, the grades similar to 303, 304, 316, 321, 347,
416, and 440 were brought to market.
In the early stages of their production, stainless steels were melted using an electric arc furnace.
Stainless steels were made to contain no more than 0.12% carbon. A large fraction of production
of stainless steels was melted to a maximum carbon content of 0.07 or 0.08%.
In those early days, carbon steel scrap, iron ore, and burnt lime were charged into an electric arc
furnace. After the scrap was molten, carbon was removed by adding ore until the carbon content
reached 0.02%. The electrodes were then raised and the slag removed as completely as possible.
Desired amounts of ferrosilicon, burnt lime, and fluorspar were added and the temperature of the
bath was raised so that a large amount of low carbon ferrochromium could be added to achieve the
aim chromium level. The desired amount of the low carbon ferrochromium was added in two or
three separate batches. The bath had to be mixed thoroughly by rabbling or reladling and slag had
to be kept fluid by continuous additions of ferrosilicon, lime and fluorspar. After all the desired
chromium was in the alloy, a sample was taken for preliminary analysis. Final additions were made
and the heat was brought to the desired tapping temperature and tapped.1
Until about 1970, the majority of stainless steel was produced in the arc furnace. With the advent
of tonnage oxygen production, the electric furnace stainless steel melting practice changed from
the above. Gaseous oxygen could be used to improve the rate of decarburization. This could be
achieved by injecting oxygen gas into the liquid steel using a water-cooled lance. The faster oxidation of carbon with high oxygen potential was accompanied by the adverse reaction of extensive
oxidation of chromium to the slag. This necessitated a well-defined reduction period in which ferrosilicon was used to reduce the oxidized chromium from the furnace slags.
In the late 1960s, a number of laboratory studies were performed to understand the thermochemistry of the stainless steels.2 One of these studies was by Krivsky, who studied the carbonchromium-temperature relationships. His experiments involved blowing oxygen onto the surface
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Steelmaking and Refining Volume

of the baths of molten chromium alloys. He was trying to perform the experiments under isothermal conditions but found it difficult because of the exothermic nature of the oxidation reactions.
Krivsky added argon to oxygen in order to control the temperature. He found that with argon dilution he could decarburize the melt to even lower levels of carbon without excessive oxidation of
chromium.3
Krivskys observations led to initial experiments where argon-oxygen mixtures were injected
through a lance into the bath in the arc furnace. It was found that argon injection in the wide and
shallow bath of an arc furnace did not influence the decarburization reaction completely as predicted. Hence, after many experiments, the developers decided that a separate refining vessel was
necessary to develop a commercial process. At Joslyn Steel (now Slater Steels), a 15-ton converter
with three tuyeres was built. The first successful heat was made in October 1967. These successful trials led to patents for the argon-oxygen decarburization (AOD) process for the refining of
stainless steels and other specialty alloys4 by the industrial gases division (now Praxair, Inc.) of
the Union Carbide Corporation.
The AOD process revolutionized stainless steelmaking. It lowered the cost of production of
stainless steels significantly. It allowed operators to use electric arc furnaces for melting down of
1996

1983

AOD
71.8%

AOD
68.7%
4.2% EAF

6.8% VOD

9.2% VOD

5.0% Converter

4.4% Converter
19.5% Converter / VOD

10.4% Converter / VOD


Fig. 12.1 Stainless steel production by process for two selected years.

stainless and carbon steel scraps with desired


amounts of low cost high carbon ferrochromium.
The decarburization operation was moved out of
the electric furnace and into the newly designed
converter. The oxidation-reduction operation
could be conducted at very high productivity
rates. Additionally, the quality of the alloys produced was improved. The process was adopted
by major stainless producers at a very rapid rate.
As shown in Fig. 12.1, the AOD process is the
predominant method for making stainless steel
in the world.5 A schematic of a modern AOD
vessel is shown in Fig. 12.2.
Duplex processes are used for making stainless steels. There is an electric arc furnace or
similar melting unit that melts down scrap, ferroalloys and other raw materials to produce the
hot metal. The hot metal, which contains most
716

Top lance
(O2, Ar, N2)

Gases
(Ar, O2, N2, air)

Fig. 12.2 AOD vessel.

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Refining of Stainless Steels

Top lance - process gas

Cooling scrap
Alloying material
Burnt lime

O2
Ar
Sublance

N2
Waste gas

Tuyereprocess gas

O2, H2O (steam), N2

Fig. 12.4 CLU vessel.


O2
Ar
N2

Fig. 12.3 Schematic of KCB-S process.

of the chromium and nickel as well as some other alloying elements, is the charge to the converters. The converters are used to achieve low carbon stainless steels which may be tapped into a
teeming ladle. The EAF-AOD process is one such duplex route. The versatility of the AOD process
led steelmakers to re-examine the use of different converters for melting of stainless steels. This
led to the development of several other converters for duplex processes. These include: KCB-S6
process developed by Krupp Stahl, shown in Fig. 12.3; K-BOP7 process used by Kawasaki Steel
Corporation; K-OBM-S8 promoted by Voest Alpine; metal refining process (MRP)9 developed by
Mannesmann Demag; Creusot-Loire-Uddeholm
Reduction mix bin
(CLU)10 process, shown in Fig. 12.4; Sumitomo
11
top and bottom (STB) blowing process by
Sumitomo Metals; top mixed bottom inert
up / down
(TMBI)12 process used by Allegheny Ludlum
Corporation; VODC13 process tried by Thyssen
Standby
where vacuum is applied to the converter; and
14
AOD/VCR process developed by Daido,
shown in Fig. 12.5.
Vacuum lid
The development work to make stainless steels
using conventional BOF converters had begun
in the late 1950s and early 1960s. By the mid1960s, some steelmakers were using existing
BOF converters for a partial decarburization
followed by decarburization in a ladle under
vacuum to make the low carbon stainless
steels. These processes are known as triplex
processes because three process units, such as
electric arc furnace, a converter for pre-blowing, and a vacuum decarburization unit for
final refining, are involved. The steels undergo

Fig. 12.5 AOD/VCR vessel.

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Steelmaking and Refining Volume

treatment for final decarburization, final trimming, homogenization and flotation of inclusions
before the ladle is taken to the teeming operation. In almost all of these triplex processes, vacuum
processing steels in the teeming ladle is the final step before casting. The vacuum oxygen decarburization (VOD) process was developed by Thyssen in West Germany.15 The other processes using
vacuum include the use of RH-OB for making stainless steels at Nippon Steel Corporation16 and the
use of an SS-VOD process17 by Kawasaki Steel Corporation. These processes are shown in Fig. 12.6.
With all these developments over several decades, now there are many different processes to make
stainless steels. The available processes can be divided into three groups: the converter processes,
converter with vacuum processes, and vacuum processes. Table 12.1 shows the variety of
processes.
Table 12.1 Different Process Routes for Making Stainless Steels
Process
AOD
KCB-S
K-BOP/K-OBM-S
MRP, ASM
CLU
AOD-VCR (vacuum)
VOD (vacuum)

Tuyere Location
Side
Side
Bottom or Side
Bottom
Bottom
Side
Bottom (bubbler)

Bottom Gases
O2, N2, Ar, Air, CO2
O2, N2, Ar
O2, N2, Ar, Hydrocarbons
O2, N2, Ar
O2, Steam, N2, Ar
O2, N, Ar2, N2, Ar
Ar, O2

Top Gases
O2, N2, Ar
O2, N2, Ar
O2, N2, Ar
O2, N2, Ar

O2 lance
O2 lance

to
vacuum

Ar
Ar
Oxygen
blowing
lance

VOD

CO CO

Tank VOD
or SSVOD

Post-combustion
CO(g) + 1/2O2 = CO2 + Q
[C] + 1/2O2 = CO(g)

[C] + [O] = CO(g)

Ladle

RH-OB

Fig. 12.6 Vacuum processes for refining stainless steel.

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Refining of Stainless Steels

A worldwide survey of the steel companies using one of these processes to make stainless steels is
given in Table 12.2. Only the companies with process vessels larger than 20 tons are considered. A
number in parentheses indicates the number of similar converter vessels currently operated by the
company. A slash indicates the company also uses another process. Companies that have known
vacuum processing capability are noted. This list is by no means comprehensive.
Table 12.2 Survey of Steel Companies and Processes Used
Company

Converter

Acenor Inoxydales Olarra


Aceria de Alava
Acerinox S.A.
Acesita
Aichi
Allegheny Ludlum Corp.
ALZ
Armco Advanced Materials
Ashoka
Atlas Specialty Steels
Aubert et Duval
Avesta-Sheffield
Boschgotthardshutte
Carpenter Technology Corp.
Cheliabinsk
China Steel
Cogne
Columbus
Crucible Materials Corp.
Daido
Electralloy Corp.
Erasteel Commentry
Ferro Alloys Corp. (Facor)
Ferrometals
FirstMiss Steel Inc.
Foroni
Inco Alloys Inter., Inc.
Isibars
ISPL Industries Ltd.
J&L Specialty Products
Jindal Strips
Jorgensen Forge
Kawasaki
Keshari Steels
Krupp Thyssen Nirosta Terni
Kusum Ingots & Alloys
Latrobe Steel Co. (Timken)
Lukens
Maharashtra Elektro
Mardia Ispat Ltd.
Mardia Steel II Ltd.
Metarom
Microsteel
Mukand Ltd.

AOD
AOD
(2) AOD
AOD/MRP-L
(2) AOD
AOD
MRP
(2) AOD
AOD
AOD
AOD
(3) AOD/CLU
AOD
(3) AOD
KCB-S
LD
AOD
AOD/CLU
AOD
(2) AOD/AOD-VCR
(2) AOD
AOD
ASM
CLU
AOD
AOD
AOD
ASM
ASM
AOD
(2) ASM
AOD
K-BOP
ASM
(5) AOD
ASM
AOD
AOD
CLU
AOD
ASM
AOD
K-OBM-S
ASM

Vacuum

VOD

VOD

(2) VOD

VOD

VOD

VOD
VOD

VOD

VOD
VOD
VOD
continued

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Table 12.2 Survey of Steel Companies and Processes Used (continued)


Company

Converter

Vacuum

Nippon Metal Industries


Nippon Steel Corp.
Nippon Yakin Kogyo
Nisshin Steel
Nova Udyog Ltd.
Nucor Steel Corp.
Outokumpu Oy
Pacific Metal (PAMCO)
Paliwal Ministeel
Panchmahal
Pohang Iron and Steel (POSCO)
Prakash Industries
Rathi Alloys and Steel Ltd.
Rathi Ispat
Republic Engineered Steels
Sandvik, A.B.
Shanghai #3
Shri Ishar
Slater Steel Corp. (Joslyn)
Sumitomo Metals Industry
Tang Eng Iron Works (TESSP)
Ugine
Universal Stainless
Valbruna
Vardhmaw Special
Walsin-Cartech
Yieh United
Yodogawa Steel Works

(2) AOD
AOD
AOD
LD
OTB
AOD
(2) AOD
(3) AOD
AOD
ASM
AOD/K-OBM-S
ASM
AOD
AOD
AOD
AOD

(2) VOD
VOD
VOD

VOD

VOD
MRP
AOD
(2) AOD
AOD
(3) AOD
AOD
AOD/K-OBM-S
ASM
MRP-L
MRP-L
AOD

VOD
VOD

VOD
VOD

In the following sections, the various processes for making stainless steels are discussed. First,
there is a brief discussion of the general principles of refining stainless steels, followed by an
examination of process routes. Then the melting of scrap and raw materials is described. Melting
methods are common to all the duplex and triplex routes for making stainless steels. Most steel
plants use electric arc furnaces for melting scrap and raw materials. Alternative technologies such
as a direct current furnace, a plasma furnace or a similar melting unit can serve the same purpose.
The balance of the chapter is devoted to a discussion of refining methods.

12.2 Special Considerations in Refining Stainless Steels


As discussed in Chapter 2, stainless steel decarburization must account for or minimize the oxidation of chromium. It is generally accepted, that when oxygen is injected into stainless steel, a mixture of chromium and iron is oxidized.18, 19 Decarburization occurs when dissolved carbon reduces
the chromium and iron oxides that form. The decarburization sequence is thus:
3/2O2(g) + 2Cr Cr2O3

(12.2.1)

Cr2O3 + 3C 2Cr + 3CO(g)

(12.2.2)

Decarburization occurs on the surface of rising bubbles that form from either the inert gas that is
injected or on the suface of chromium oxide particles that are being reduced and generating CO.
The decarburization of stainless steel involves techniques to minimize chromium oxidation. There
are three basic techniques: temperature, dilution, and vacuum.
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Refining of Stainless Steels

The temperature technique was used by electric arc furnace stainless steelmaking before the development of duplex methods. As shown in Chapter 2, Section 2.9.1, as the temperature increases, the
equilibrium carbon content at a particular chromium content decreases. As discussed above, however, this leads to operational difficulties and high costs.
The dilution technique is that used by the AOD and all converter processes. The injection of inert
gas (argon or nitrogen) lowers the partial pressure of CO in the bath, thus allowing higher chromium
contents to be in equilibrium with lower carbon contents, as shown in Chapter 2, Section 2.9.1.
Applying a vacuum to the metal bath also removes CO, allowing high chromium contents to be in
equilibrium with low carbon contents. It is especially effective when the carbon content is low.
Careful manipulation of the slag, as it participates in the reaction, is important. Any chromium
oxide not reduced by carbon ends up in the slag, which can form a complex spinel. Subsequent processing (called reduction) is required to recover oxidized elements such as chromium, iron, manganese, etc. The effectiveness of the reduction step is dependent on many factors including slag
basicity and composition, temperature, mixing conditions in the vessel and solid addition dissolution kinetics.20 Chapter 2, Section 2.9.3 describes these reactions in more detail.

12.3 Selection of a Process Route


As outlined earlier, there are many different process routes available for stainless steel melting and
refining. The steelmaker has to choose from these routes based on many factors which determine
capital costs as well as operating costs. The choice of process route is influenced by raw material
availability, desired product, downstream processing, existing shop logistics, and capital economics.
In general, some degree of flexibility in process route is desirable, as these factors can change
rapidly. In general, stainless steelmaking process flow can be classified as duplex or triplex. The
comparison of these two processes is shown in Fig. 12.7. Duplex refining, where electric arc furnace
O2, N2, Ar

Scrap
FeCrHC
Ni

O2
N2 / Ar

O2, N2, Ar
LPG

Duplex route

Ar

Triplex route
Ar
Fig. 12.7 Comparison of duplex and triplex process route in stainless steelmaking.
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melting is followed by refining in a converter, tends to be flexible with respect to raw material
selection. Triplex refining, where electric arc furnace melting and converter refining is followed by
refining with a vacuum system, is often desirable when the final product has very low carbon and
nitrogen specifications.21 Triplex refining tends to have overall cycle times longer than duplex
refining because there is an extra transfer from refining converter to vacuum unit. It also tends to
have slightly higher refractory costs because there are two vessels performing decarburization.
Raw material availability affects the choice of process route. For example, high argon costs shift
the economics of stainless production away from dilution type processes in favor of vacuum
processes. A lack of scrap forces the use of more high carbon ferrochrome, increasing the carbon
load in the charge. In such a case, process routes that have high decarburization rates would be
favored. Lack of scrap, which can be used for cooling the bath, also can favor processes that are
not thermally efficient, as there is no economical addition for cooling the bath. Where scrap and
ferroalloys are expensive or unavailable, process routes have been developed that use chromium
ore and blast furnace or similar hot metal.22, 23 These processes typically incorporate a smelting
unit, often a converter, to reduce the ore, followed by decarburization in another converter, possibly followed by vacuum processing.
The desired product mix affects the choice of process. High production levels of ultra low carbon
and nitrogen stainless steels tend to favor vacuum processes to avoid high argon consumption. For
typical levels of carbon and nitrogen in stainless steels, the processing cost are usually lower for
the converter processes than vacuum or triplex processes.
Downstream processing considerations also will affect the choice of process. Sequence continuous
casting requires a stainless steel refining route that will provide feed metal at the proper temperature, composition and time to sequence cast.
Availability of ladle furnaces and ladle stations can shift some of the non-decarburization time
from the refining vessel to the ladle furnace or station. Some high productivity shops tap the heat
out of the converter just after the reduction stage. The final additions are made to the ladle. This
frees up the refining vessel for the next heat.
If existing melting capacity is insufficient for desired production levels, the refining process may
need to melt large amounts of cold material. This would favor processes that are thermally efficient
or ones that can generate heat for melting. If melting is primarily by induction furnaces, raw material choices may be limited. Blast furnace or hot metal availability would also influence the type
of refining process. Available vacuum or baghouse capacity may influence the choice between vacuum or dilution methods. Crane capacity may limit vessel size. Crane traffic and shop layout will
affect process flow. Existing ladle cars can help or hinder material movement. An existing continuous caster also would affect process choice.
Cost of capital always affects process choices. Systems for making alloy additions can be very expensive. Baghouse and vacuum capacity is also expensive. There is often a balance between capital and
operational cost. The process with the lower operating cost sometimes has the highest capital cost.
In some recent installations, capital spending considerations have eclipsed those of all other factors, including flexibility and operating costs, in the selection of process route. For major turnkey
installations, which may include steel melting, refining, casting, hot and cold rolling, anneal and
pickle lines, as well as the associated technology, the choice of equipment suppliers is limited to
three or four large firms. Each of these suppliers aggressively promotes its own secondary steelmaking process as superior relative to operating costs, quality, productivity, etc. However, several
of these suppliers will manufacture and install a version of any other type of secondary steelmaking, if the customer insists. Depending on geographical location, order backlogs, previous equipment sales, manpower availability, etc., any one of these suppliers may be in a better position to
manufacture and install equipment at a substantially lower price than the others.
For maximum flexibility, a shop should have a process flow that can incorporate a duplex or triplex
route. This offers the most flexibility in raw materials, production capability, and process flow. In
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Refining of Stainless Steels

this case, only products that require vacuum refining for economic and/or quality reasons will use
a triplex route.

12.4 Raw Materials


Raw materials used in all stainless steel making operations can be divided into two main groups;
nonmetallic raw materials and metallic raw materials. The nonmetallic materials typically needed
are burnt lime, dolomitic lime and flurospar. The metallic raw materials needed are stainless steel
scrap, carbon steel scrap and a variety of alloying materials and deoxidizers. The major alloying
materials used are chromium, nickel, manganese and silicon additives.
Ferrochromium is the prime source of chromium and it comes in a range of addition agents. The
common chromium alloying materials charged to the electric arc furnace and AOD are given in
Table 12.3.
Table 12.3 Raw Materials Used to Supply Chromium Units
Chromium Additive

Carbon

Chromium

Silicon

Low Carbon Ferrochromium


Medium Carbon Ferrochromium
Low C, Low N2 Ferrochromium
Simplex Ferrochromium
Intermediate Carbon Ferrochromium
High Carbon Ferrochromium
High Carbon Ferrochromium
Ferrochromium-Silicon

0.10
0.13
0.045
0.01
2
7.4
7.7
0.055

69
70.7
67.8
69
55
68.7
69.2
37

0.9
0.9
0.63
0.28
0.1
0.85
0.17
40

Nitrogen

Manganese

0.01

0.2
0.45
0.15
0.22
0.16
0.27

Nickel is present in significant amounts in the AISI 200 and 300 series stainless steels. In addition
to austenitic stainless steel scrap, nickel is available as electrolytic nickel, nickel powder, nickel
oxide, briquetted nickel and ferronickel. Typical analyses of nickel containing raw materials are
given in Table 12.4.
Table 12.4 Raw Materials Used to Supply Nickel Units
Nickel Additives

Carbon

Nickel

Silicon

Cobalt

Sulfur

Chromium

Copper

Nickel Briquettes
Low Carbon Nickel Shot
High Carbon Nickel Shot
Nickel Pig
Nickel Copper Shot
Nickel Oxide Sinter

0.01
1.64
0.07
0.3

99.9
50
28
39
51
75

0.02
1.4
0.4
0.1

0.78
0.6
0.7

0.007
0.06
0.015

0.007
0.7
0.15
1.2

26.5

Manganese is present in significant amounts in the AISI 200 series of alloys. Sources of manganese
are given in Table 12.5.
Table 12.5 Raw Materials Used to Supply Manganese Units
Manganese Additives

Carbon

Manganese

Silicon

Electrolytic Manganese
Ferromanganese
Manganese-Silicon

7.1
0.07

99.99
79
61

0.05
31

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Silicon is used in all the stainless steel making processes to chemically reduce the chromium which
is present in the slag at the end of the decarburization period. For this purpose, silicon is added in
the reduction mix as ferrosilicon or ferrochromiumsilicon. Additional silicon would be needed to
meet any silicon specification on many of these stainless steels. The most common raw materials
used to supply the silicon are its ferroalloys which contain nominally either 50% silicon or 75%
silicon.
Molybdenum is added to some of the stainless steel grades. The materials which can be used to add
molybdenum include molybdenum oxide in powder or briquette form and ferromolybdenum.
Aluminum is a common deoxidant and high purity aluminum pig or bar is added for this purpose.
Titanium is a very frequent addition to many stainless steel grades for the purpose of stabilization
(see Chapter 11). The most commonly used alloys of titanium are 70%Ti30%Fe and
90%Ti4%V5%%Al alloy. The other elements which are generally added in the ladle include carbon, sulfur, nitrogen, niobium (columbium), tungsten and copper. Selenium and tantalum are
added to a very limited number of grades.
In stainless steelmaking, most of the cost of the final product is due to raw materials. Over more
than the past two decades, computer programs, most of which use linear programming techniques,
have been developed and used to utilize the raw materials in such a way that the total raw material
cost of production is minimized.

12.5 Melting
For the electric arc furnace, typical charges are scrap and ferroalloys. As there is further refining,
least cost charges incorporate high carbon ferroalloys for chromium and manganese units.
Usually, the least cost source of material is used; for scrap this may consist of oily turnings and
furnace skulls.
Sometimes, hot metal from the blast furnace or other iron source is available. In this case, the
electric arc furnace can be used to melt only ferroalloys with the resulting melt then mixed with
the molten iron in a converter process for refining.22 The electric arc furnace can also be bypassed
altogether.
When hot metal is the source and stainless scrap or ferroalloys are unavailable or too expensive,
then chromium, manganese and nickel ores can be used as sources of material.23, 24

12.5.1 Electric Arc Furnace Melting


The delivery of molten material for further processing requires melting facilities of some kind. The
electric arc furnace is by far the most popular choice due to its flexibility of raw material sources
and widespread use. Induction melting is popular in smaller shops and foundries; however, it is less
capable of handling some scrap sources, such as turnings and oily scrap.
The job of the melter, be it electric arc furnace or other method, is to melt down the basic raw materials as quickly and economically as possible. The potential of chromium oxidation places some
limits on the use of oxygen injection into the arc furnace. Carbon injection and foamy slag practices, while common in the carbon steel industry, are rarely employed in stainless steels. The slags
that form in the melting of stainless are high in chromium oxide and are not as fluid as carbon steel
slags. The stainless steel melt slags do not foam as easily.25 CO generation for formation of the
foamy slags also does not occur if the chromium content is high.
Stainless steel melt charges in the United States are primarily scrap based. Scrap stainless steel is
often a cheaper source of chromium and nickel units than virgin material such as ferrochromium
and nickel.
Melting of stainless steel is a choice of the least cost sources of metal units. There is usually some
consideration of impurities such as copper and phosphorus, which are not removed during subsequent processing.
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Refining of Stainless Steels

For a 300 series stainless steel, a typical melt-in mixture might consist of: 50% 300 series scrap
(18%Cr, 8%Ni, 1%Mn); 30% carbon steel scrap;14% high carbon ferrochrome (7%C, 65%Cr); 4%
nickel (commercial purity); and 1% high carbon ferromanganese (7%C, 65%Mn).
At melt-in, this mixture would yield about 18%Cr, 8%Ni, 1%Mn and 1%C.
In the early stages of melting, some shops will use burners and oxygen lancing. The added energy
input increases the melt-in rate in the early stages of melting. After the second bucket however,
burner and oxygen use is limited to avoid chromium oxidation. At tap, ferrosilicon is often added
to recover oxidized chromium from the slag.

12.5.2 Converter Melting


Converter melting requires oxygen and carbon injection coupled with post-combustion to generate
heat. Converter melting is rarely economical but high electrical power costs or lack of electric melting capacity, combined with hot metal availability, may make this option viable.
In converter melting, molten hot metal is charged into a smelting converter and the ores added.
Carbon is also injected or charged as the reductant and as fuel. Oxygen is injected by a lance for
burning carbon and post-combustion. This generates the heat necessary for the smelting reaction.
Ores typically contain some amount of gangue, so appropriate slag conditioners are also added.
The slag is decanted and the metal, now close to the desired composition, is transferred to another
converter for refining.

12.6 Dilution Refining Processes


The melting processes supply the liquid stainless steel, which now contains desired amounts of
chromium, nickel and other alloying elements, to the next process step. The latter is directed at
decarburizing the stainless steel alloy to the desired carbon content. It is accompanied by oxidation
of chromium, iron, silicon, aluminum, titanium and manganese which are present in the charge. In
a converter, decarburization is carried out using the dilution principle. There are different converters based on the gases used. Another difference is whether the vessel is side or bottom-blown.
Proponents of side blowing argue that side blowing results in higher carbon removal efficiencies
(amount of oxygen reacting with carbon divided by the total amount of gases blown) in the range
of 0.1 to 0.005% carbon, due to longer inert gas bubble residence time, and improved desulfurization in the range of 0.005% to less than 0.001% sulfur due to improved mixing.
The most popular converters for making stainless steels are AOD, KCB-S, K-BOP/K-OBM-S,
MRP and CLU. Each of these are discussed in the following sections.

12.6.1 Argon-Oxygen Decarburization (AOD) Converter Process


The AOD process, shown in Fig. 12.2, is used for the production of stainless steel in the second
step of a duplex process. The molten steel, which contains most of the chromium and nickel needed
to meet the final heat composition, is tapped from the electric arc furnace into a transfer ladle. The
transfer ladle is lifted with a crane and the liquid steel is poured into the AOD vessel. The vessel
can be rotated downwards so that the side mounted tuyeres are above the bath level during charging of the liquid steel. In the early days of the AOD process, the vessel was tilted for making raw
material additions as well as for taking samples and temperature measurements using immersion
thermocouples. The desire to increase the productivity has led to continuous charging of raw materials during the blow periods as well as reduction periods. Modern instrumentation has been developed which can take melt samples as well as steel temperatures using a specially designed
sub-lance with the vessel in the upright position.
Typical consumptions26 of an 80-ton AOD making AISI 304 are shown in the Table 12.6.
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Table 12.6 Typical Consumptions

Argon
Nitrogen
Oxygen
Lime
Spar
Aluminum
Silicon (reduction)
Brick
Decarburization metallics
Charge to tap time
Total Cr yield
Total Mn yield
Total Metallic yield
*1.8%

Units

Typical

Best

Nm3/ton
Nm3/ton
Nm3/ton
kg/ton
kg/ton
kg/ton
kg/ton
kg/ton
kg/ton
min.
%EAF/AOD
%EAF/AOD
%EAF/AOD

12
911
2532
5060
3
2
89
59
135
5080
9697
88
95

9
9
NA
42
2
1
6
2
NA
40
99.5
95
97

start carbon, 0.05% Nitrogen, 0.005% Sulfur

A major modification of the original AOD process involves the use of a top-blowing lance in addition to the side blowing tuyeres. The lance can be used to inject oxygen at desired flow rates to
increase decarburization and/or for post-combustion. The top lance can also be designed for blowing mixed gases such as inert-oxygen gas mixtures. The installation of a lance and introduction of
oxygen in the early stages of decarburization can reduce the time for a heat. The technology can
be used to increase productivity, in tons per hour, of a melt shop.
Another modification of the AOD involves applying vacuum on the converter to reduce the argon
and silicon consumption as well as process time when making low carbon grades. This modification is identified as AOD-VCR and is used by Daido Steel, Japan.

12.6.2 K-BOP and K-OBM-S


Kawasaki Steel Corporations K-BOP process began as a conventional top oxygen blown BOF. It was
modified to have seven bottom tuyeres of the OBM (Q-BOP) type. These tuyeres could blow oxygen
with propane for tuyere cooling. Powdered lime could also be injected through these tuyeres.
In its initial development stage, an 85 ton ultra-high-powered electric arc furnace (UHP-EAF) was
used to supply the hot metal to the reactor. The top and bottom oxygen blowing was used to achieve
high decarburization rates.27
Kawasaki Steel Corporation continued the developmental work where chromium ore and coke
were added to the reactor. The reactor was thus used for reduction of chromium ore and after that
switched over to decarburization operation. Additional developmental work at Kawasaki Steel led
to a smelt reduction process for stainless steelmaking using separate reactors. Final decarburization (below 0.10%C) was carried out in a top-blown RH degassing unit (the KTB process).
Eventually a process using separate converters and a VOD unit was developed. The later development is discussed later in Section 12.8 on direct stainless steelmaking.
The K-OBM-S process developed by Voest Alpine Industrieanlagenbau (VAI) and evolved from
Kawasakis K-BOP process. The K-OBM-S process initiated with tuyeres installed in the converter bottom. However, two recent installations, POSCO in Korea28 and Bolzano in Italy, are
side-blown reactors.29 Thus, a K-OBM-S converter is top-blown with a lance and bottom or sideblown with tuyeres. It is very similar to a modern AOD. However, in the K-OBM-S process,
hydrocarbons, such as natural gas or propane, are used for tuyere protection and this can be
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Refining of Stainless Steels

helpful in increasing the refractory life. Typical consumptions and conditions 21 for making AISI
304 are given in Table 12.7.
Table 12.7 Consumptions and Conditions for AISI 304
Condition/Addition

Units

Typical Values

Aim carbon
Aim nitrogen
Melt-in carbon
Melt-in silicon
Oxygen
Nitrogen
Argon
Silicon (reduction)
Lime
Dolomite
Fluorspar

%
ppm
%
%
Nm3/ton
Nm3/ton
Nm3/ton
kg/ton
kg/ton
kg/ton
kg/ton

0.033
300
1.77
0.13
29.5
13.2
16.5
11.1
51
20
7.9

12.6.3 Metal Refining Process (MRP) Converter


The metal refining process was developed by Mannesmann Demag Huttentechnik. It is also a
duplex process where scrap and raw materials are melted in an electric arc furnace or similar unit.
Molten metal, which contains chromium and nickel, is charged to the MRP converter.
Decarburization is carried out using oxygen and inert gases. In early stages of development, the
gases were alternately blown through the tuyeres in the bottom of the reactor.30, 31 The oxygen is
blown into the melt without dilution with any inert gas. The desired oxygen blow is followed by
blowing with inert gas only. The cycle of oxygen blow followed by inert blow is called cyclic refining or pulsing and the developers claim that the flushing with pure inert gases can lead to achieving low CO partial pressure and faster decarburization and thus lower chromium oxidation and
consumption of silicon for reduction. The original version of the converter has now evolved into
the MRP-L process in which all oxygen is top-blown and inert gas is injected through the porous
elements in the bottom.
The developers claim that the process can use higher blowing rates than those used in the AOD
process, which has sidewall tuyeres. The bottom tuyeres can be replaced easily through the use of
an exchangeable bottom. With bottom tuyeres, there is less likely to be erosion on the sidewalls of
the vessel.
In recent years, the MRP-L units have been coupled with a vacuum unit as part of the triplex
process for making stainless steels, especially those requiring lower carbon and nitrogen levels. In
these plants, the heats are tapped at an intermediate carbon level appropriate for subsequent vacuum decarburization.

12.6.4 Creusot-Loire-Uddeholm (CLU) Converter


The CLU Process is similar to the AOD process for making stainless steels. It also uses liquid steel
from an electric arc furnace or similar melter. The major impetus for its development was the idea
to substitute steam as the diluting gas rather than argon. The process was developed by Uddeholm
of Belgium and Creusot-Loire of France. The converter is bottom-blown thus differentiating it from
the side-blown AOD converter. The first commercial plant using the CLU process was built in 1973
by Uddeholm, now a part of Avesta-Sheffield Stainless Co. The process is also used by Samancor
in South Africa for the production of medium carbon ferrochrome. Columbus Stainless in
Middleburg, South Africa chose this process, supplied by VAI, for their newest stainless plant,
which came on stream in 1996.32
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The decarburization period consists of injecting an oxygen-steam mixture. The process is energy
inefficient as the reaction of steam with the molten steel bath is endothermic. Chromium oxidation
is higher than in the AOD process when decarburization is continued below about 0.18% carbon.
Although the original goal of reducing argon consumption can be met, the increased silicon
requirement for the reduction step does not necessarily lead to overall cost savings. Further, the use
of steam throughout the entire period was found to lead to undesirable hydrogen contents in the
refined steel. Therefore, practices have evolved which use various amounts of steam, argon, and
nitrogen in the process. Consumptions and conditions32 for two grades are given in Table 12.8.
Table 12.8 Consumptions and Conditions for AISI 304 and AISI 409
Condition/Addition

Units

AISI 304

AISI 409

Aim carbon
Aim nitrogen
Melt-in carbon
Melt-in silicon
Oxygen
Nitrogen
Steam
Hydrogen
Argon
Silicon (reduction)

%
ppm
%
%
Nm3/ton
Nm3/ton
Nm3/ton
ppm
Nm3/ton
kg/ton

0.03
350
1.65
0.2
27.7
13.5
10.4
5.9
7.0
15.5

0.01
100
0.96
0.13
22.4
1.7
6.0
3.8
17.1
15.9

12.6.5 Krupp Combined Blowing-Stainless (KCB-S) Process


The production of stainless steels in the BOF converter using the top lance was being practiced
prior to the advent of the AOD Process.33, 34 After introduction of the AOD process, Krupp Stahl
AG modified the converter at its Bochum Works so that combined blowing through the lance and
tuyeres could be practiced for refining stainless steels. The process was named Krupp combined
blowing-stainless or KCB-S. The simultaneous introduction of process gases helped them increase
the decarburization rate. The blowing through a top lance and through the tuyeres below the bath
surface helped achieve very high decarburization rates. The increased decarburization rate led to a
reduction of up to 30% in the refining times compared to a conventional AOD alone. 28 The
schematic diagram of the KCB-S process is shown in Fig. 12.3.
Liquid steel from an electric arc furnace is charged to the converter. At the start of the blow, pure
oxygen is injected simultaneously through the lance and sidewall tuyeres. After a desired process
temperature is reached, various additions are made during the blow. The additions consist of lime,
ferroalloys, and scrap. After a critical carbon level is reached, the oxygen content of the process gas
is reduced by using inert gases such as nitrogen or argon. Oxygen to inert gas ratios of 4:1, 2:1, 1:1,
1:2 and 1:4 are used as decarburization to lower levels is pursued. When the carbon content of
0.15% is reached, the use of the lance is discontinued and the process gases are introduced only
through the tuyeres. When the desired aim carbon level is reached, the oxygen blow is discontinued and silicon is added as ferrosilicon to reduce the chromium oxide in the slag and to achieve the
required silicon specification. The addition of lime and other fluxing agents with the ferrosilicon
leads to lowering of the dissolved oxygen content and enhances the desulfurization.

12.6.6 Argon Secondary Melting (ASM) Converter


This process was developed by MAN GHH in Germany.35 It is similar to the AOD process, except
that the tuyeres are in the bottom of the vessel. When using top-blown oxygen, it is identified as
the ASM-L process.
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Refining of Stainless Steels

12.6.7 Sumitomo Top and Bottom Blowing Process (STB) Converter


Sumitomo Metal Industries developed the Sumitomo top and bottom blowing process (STB). It
was developed to overcome the disadvantages of a pure top or pure bottom blowing process by
combining the two concepts into one process.36, 37 It also tried to overcome two disadvantages of
the AOD process at the time: tuyere erosion and limited oxygen flow rate. The additional supply
of oxygen rich gases from the top lance led to shorter decarburization times compared to the AOD
process as practiced in late 1970s. The process was developed in a 250-ton converter in the No.2
steelmaking shop at Kashima Works. The process was renamed Sumitomo metal refining (SMR)
and used for a short time in the 160 ton converter at Wakayama Works.

12.6.8 Top Mixed Bottom Inert (TMBI) Converter


Allegheny Ludlum Corporation used a BOF converter to make ferritic stainless steels whenever
incremental stainless steel capacity was necessary.38 In the early stage of development, oxygen,
and oxygen-argon mixtures were introduced through a supersonic top lance. However, the process
was less efficient than the AOD process. Consequently, one BOF converter was equipped with bottom tuyeres to inject only inert gases such as argon or nitrogen. The majority of the process gas
was introduced through the top lance. The top lance could be used to introduce the desired mixture
of gases. The process was called top mixed bottom inert (TMBI). The process is similar to the other
processes that use combined gas blowing in a converter. The particular plant operated by Allegheny
Ludlum has coreless induction furnaces that melt carbon steel scrap and supply chromium-free hot
metal to the BOF converters.

12.6.9 Combined Converter and Vacuum Units


The converter processes discussed above have one disadvantage in that stainless steels with very
low carbon and nitrogen residuals become difficult to produce. The decarburization period
becomes longer while chromium oxidation and argon consumption increase as the desired carbon
and nitrogen levels decrease. Some steelmakers have tried to overcome this disadvantage by applying vacuum to the converter at the very late stages of the decarburization process. The concept was
tried in an evacuated BOF by Thyssen in the early 1970s. The concept was also promoted by
Leybould-Heraus as an alternative to AOD or VOD. The concept of applying vacuum to a converter
is being pursued by the installation of AOD/VCR by Daido at Shibukawa and Chita39 plants and
by Nippon Steel at its Hikari works.40 A schematic of the converter was shown earlier in Fig. 12.5.
The AOD-VCR operates as a conventional AOD down to 0.080.10%C. The process is stopped for
sampling and a vacuum lid is put into place. The lid is sealed to a flange located about half way up
the conical section of the converter. A vacuum is pulled and used for the remainder of decarburization and reduction. Desulfurization is carried out in the transfer ladle prior to AOD charge. The
major advantages of this process relative to converter processes are decreased argon and silicon
consumption. Disadvantages include higher refractory consumption, decreased ability to melt
scrap and added maintenance and costs associated with steam production.
When compared to separate converter and VOD units, the AOD-VCR has higher operating costs
(silicon, refractory, and argon), lower productivity and higher nitrogen contents. Capital costs may
be somewhat lower than having two separate units.

12.7 Vacuum Refining Processes


The use of vacuum for decarburization of steels was developed by different steelmakers in
Germany. The early processes included RH degassing, DH degassing, and the Allegheny vacuum
refining (AVR) as a second step in the duplex process. These processes involve lowering the pressure above the steel bath to promote evolution of carbon monoxide gas. The liquid stainless steels
going into the vacuum process generally contain carbon of about 0.5% or lower. Most vacuum
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Steelmaking and Refining Volume

processes are performed in a chamber with a ladle full of metal as opposed to a separate refining
vessel used in the dilution/converter processes.
In mid 1960s, the vacuum decarburization concept was used by Allegheny Ludlum Steel
Corporation to develop the Allegheny vacuum refining process. It was used to make the regular
grades of stainless steels and lowered the consumption of low carbon ferrochrome associated with
the oxidation-reduction practice used in the electric arc furnace. This process became non-competitive with the introduction of the AOD process. In late 1970s, Allegheny Ludlum built a plant
with an AOD reactor and discontinued the use of the AVR process.
Early duplex processes where vacuum processing was used as the second step were too slow and
had very limited flexibility with respect to raw materials that could be used. The vacuum processes
could not keep up with the improving productivity of electric arc melting furnaces and the operating costs were very high. Hence, later developments focused on the use of converters to decarburize the molten metal from electric arc furnaces as a second stage followed by vacuum degassing
for the finishing stage. Such processes are known as triplex processes for making stainless steels
as they use three processes to achieve the desired finished chemistry.
Nippon Steel Corporation introduced the RH-OB process for making of stainless steels in the
Muroran Works.41 Hot metal from a blast furnace was fed to a BOF converter where the metal was
alloyed with chromium and blown down to a 0.50.6% carbon level. The final decarburization was
conducted using the RH-OB process. Nippon Steel converted an existing RH degasser, which was
used for carbon steels, so that oxygen could be injected under vacuum.
Edelstahlwerk Witten (now Thyssen) in Germany developed the vacuum oxygen decarburization
(VOD) process in the mid-1960s. In the early stages of its development, VOD was used to decarburize molten alloy from the electric arc furnace. Later, preliminary decarburization was done in a
BOF and the EAF-BOF-VOD triplex process became more productive. In early 1970s, Kawasaki
Steel Corporation modified the VOD process using multiple porous plug bubblers in the ladle.
They called this the SS-VOD (strong stirring VOD) process.42 In 1988, ALZ in Belgium modified
the facilities to make stainless steels by a triplex process consisting of electric arc furnace melting,
metal refining process-lance (MRP-L) converter, and vacuum oxygen decarburization (VOD)
process.43
The major advantages of the vacuum processes include low consumption of argon and low oxidation of chromium during the final decarburization to low carbon levels. The latter leads to less consumption of reduction elements for recovering chromium from slag. The teeming of steel from the
ladle used in the vacuum processes eliminates the pickup of nitrogen and oxygen from air that is
associated with tapping of the converters. The SS-VOD process, because of the strong stirring
achieved using multiple bubblers in the ladle, further enhanced the ability to produce even lower
levels of carbon, nitrogen and hydrogen at higher chromium levels.
A major disadvantage of VOD processing is that it is less flexible than an AOD or other converter
process with respect to raw materials usage. Typical additions to the VOD are around 48% of tap
weight. Typical vacuum treatment times are 50 to 70 minutes with start carbon contents of 0.3%,
compared with 40 to 60 minutes with a converter starting at 1.5 to 2.5%C. This added time makes
it difficult to sequence continuous casting of heats.
Many steelmakers have also realized that vacuum processes often have high operating costs and
cannot compete with the ease of operating a converter process at atmospheric pressure. However,
the vacuum processes, especially the SS-VOD process, have the unique ability of achieving lower
carbon and nitrogen levels in stainless steels which cannot be easily achieved by the AOD process
or other converter processes.

12.8 Direct Stainless Steelmaking


In recent years, there have been efforts to use chromium and nickel ores for stainless steelmaking
in lieu of the ferroalloys. In Japan, a number of companies have developed and are using such
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Copyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.

Refining of Stainless Steels

Hot metal
dephosphorization

Direct reduction
of chromium ore
and scrap melting
SR-KCB

O2

Ar
Prevention of
chromium
oxidation by
using mixed gas

Lower cost
refining for high
grade steel

DC-KCB

VOD

Fig.12.8 The KCS process for direct stainless steelmaking.

processes commercially. In particular, Kawasaki Steel Corporation (KSC) has developed a process
which smelts chromite ore (FeCr2O4 plus other oxides). Stainless steel is produced with two 160
ton converters, without any EAF operation, but using dephosphorized hot metal, chromite ore and
ferroalloys as the major charge materials. An outline of the KSC process is shown in Fig. 12.8. The
hot metal is desulfurized and then fed into a K-BOP/K-OBM vessel (SR-KCB) which is described
in Chapter 9. Chromite pellets, which are partially prereduced up to 60% chromium content by
rotary kiln, are charged to the first reactor. Coke is also charged and serves as a heat source in the
reactor. The charging rate of ore and coke and the oxygen blow rate are controlled to achieve suitable temperature for the melt.44, 45
The steel melt, which now contains about 1116% Cr and 56% C is charged to the second KBOP/K-OBM vessel. Primary decarburization (DC-KCB) is carried out using oxygen, argon and
nitrogen gases in this vessel. Top and bottom oxygen blowing is used to lower the carbon content
of the melt to about the 1% level. This is followed by mixed gas blowing only from the bottom.
This is called the DC-KCB process and is similar to a modern AOD operation. The process reduces
the carbon to about 0.15%. Final decarburization and reduction is carried out in a VOD. The
process uses less amount of scraps than the EAF-AOD process route. However, it requires liquid
hot metal from a blast furnace and more process steps and more capital investment than the EAFAOD route.
NKK Corp. has developed and commercialized a similar process which also smelts both chromite
and nickel ore.46 After hot metal dephosphorization, the metal is transferred to a smelting furnace
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731

Steelmaking and Refining Volume

and nickel ore is smelted. As a nickel ore typically contains 13% nickel, a considerable amount of
ore is added and the slag must be removed several times to achieve the desired nickel level. After
reaching the required nickel content, chromite or chromium ore is smelted. The smelting takes about
six hours; four for nickel and two for chromium. This is followed by the decarburization period.
Similar to the KSC process, the NKK process uses less scrap and only a small amount of nickel
metal and ferrochrome. However, the process requires hot metal and a very long process time.
These direct stainless steelmaking processes require less scrap and ferroalloys and may be considered when the stainless scrap and ferroalloys are not readily available in sufficient quantities.
However, chromium and nickel ores are needed and can be used in an integrated steel plant where
the hot metal is available. The processes are more capital intensive than the other processes.
Therefore, their implementation in other plants and locations is likely to be limited.

12.9 Equipment for EAF-AOD Process


The previous three sections outlined the concepts of different processes to make stainless steels.
The EAF-AOD, EAF-CLU and similar duplex process routes are the most popular for making
stainless steels. This section describes the equipment used in the EAF-AOD process route, which
is by far the most popular process in the world for making stainless steels.
For converter refining processes, the vessel consists of a refractory-lined steel shell. Several types
and qualities of basic refractory have been used in converter vessels. Refer to Chapter 4 for more
details of stainless steelmaking refractories.
Process gases are injected through submerged tuyeres that are installed in the sidewall or bottom
of the vessel. Sidewall injection imparts maximum stirring energy to the bath for greatest efficiency of mixing. Bottom injection usually improves wear characteristics in the barrel section of
the vessel. The number and relative positioning of tuyeres is determined in part by vessel size,
range of heat sizes, process gas flow rates and the types of alloys refined. Process gases are oxygen, nitrogen, carbon dioxide, air, hydrocarbons and argon. Most recent converter installations
include the use of a top lance for blowing oxygen.
The gas control system supplies the process gases at nominal rates of 1.03.0 Nm 3/min/ton
(20006000 scfh/ton). The system accurately controls the flowrates and monitors the amount of gas
injected into the bath to enable the operator to control the process and measure the total oxygen
injected. In contrast, vacuum processes typically use much lower total input rates, e.g., 0.020.6
Nm3/min/ton (typical top oxygen blow rate 0.30.4 Nm3/min/ton) and seldom use gases other than
oxygen, nitrogen and argon.
A high production shop will typically have three interchangeable vessels for 100% availability of
the process. At any given time, one of the vessels is in the tiltable trunnion ring refining steel, a
second newly lined vessel is at a preheating station, and the third vessel is at a reline station. The
vessel in the trunnion ring typically can be replaced with a preheated vessel in less than an hour.
Process gas control, vessel activities and ancillary equipment can range from manual to fully automated. Most installations are equipped with a computer for calculating oxygen requirements as
well as alloy additions. Some installations have computer controls capable of setting flow rates to
the gas control system.

12.9.1 Vessel Size and Shape


The converter vessel consists of a refractory-lined steel shell.47 With a removable, conical cover in
place, the vessel outline is sometimes described as pear-shaped. Modified BOF vessels have also
been used. As molten stainless steels do not generate foam, and most stainless steel refining
processes are side or bottom-blown, the dimensions of a stainless refining converter are smaller
than a comparable tonnage BOF or OBM (Q-BOP). Typical internal volumes of stainless steel
refining converter vessels are in the range 0.40.8 m3/metric ton bath weight.
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Refining of Stainless Steels

For vessels that tap into a ladle held by a crane, a sliced cone top section is often used. The slice
portion allows the crane to come close to the vessel mouth. Fig. 12.2 shows an AOD vessel with a
sliced cone top section. Vessels that tap into a ladle car usually have a BOF-type concentric cone
top section.

12.9.2 Refractories
High temperatures at the tuyere tip and high bath agitation place great demands on the vessel
refractory.48 While typical BOF refractory campaigns are months or years long, stainless converter
campaigns are several days or weeks long. Refractory costs are a significant fraction of total operating costs.
There are two basic choices of refractory type, magnesite-chromite, and dolomite. The choice of
refractory is dependent on the vessel operation pattern, final product specifications, and economics.
Magnesite-chromite refractories have high wear resistance but have a higher unit cost than
dolomitic refractories. Chromium pickup from the brick is possible. Magnesite-chromite bricks are
simultaneously acidic and basic and strict slag compositions must be maintained to prevent rapid
wear.49,50,51
Dolomitic refractories are usually less costly than magnesite-chromite refractories and chromium
pickup is not a factor. Desulfurization to very low levels is generally easier in dolomitic refractories because very basic slags can be used without detrimental effects to the brick.52 Most major
stainless producers in the United States and Europe use dolomitic refractories in the converter.
Vessels are typically zoned by thickness and brick quality to maximize lining life and minimize
costs. High wear areas of the vessel, usually the tuyere wall, slag line, and transfer pad (where the
metal stream strikes the vessel during transfer) are zoned thicker and with higher quality refractory
than other parts of the vessel.
For more analysis of stainless steelmaking refractories, see Section 4.4.

12.9.3 Tuyeres and Plugs


The AOD process and most other converter processes have tuyeres mounted in the sidewall or in
the bottom. These tuyeres typically consist of a copper tube with a stainless steel outer tube. An
annulus is formed between the copper and stainless tubes. Cooling gases blown through the outer
annulus (shroud) form a metal or oxide accretion (called a knurdle or a mushroom) at the tuyere
tip. This accretion protects the tuyere and surrounding refractory. Process gases of oxygen/inert
mixtures blow through the inner annulus. Special designs exist for normalizing the flow in the
annular gap.53 Tuyere size and number depend on specific process parameters. There are usually
between two and nine tuyeres in an AOD vessel.
Sidewall mounted tuyeres are submerged while processing. When the vessel is rotated, the tuyeres
are above the bath. At this point, the process gases can be shut off and a small cooling flow protects the tuyeres.
Bottom-blown vessels have a variety of tuyere configurations depending on flow rates required.
There are usually two to four tuyeres in the bottom. Most have some variation of OBM (Q-BOP)
tuyeres. Processes with low flow rates that use only inert gases, such as VOD, for the bottom-blown
gases can use a plug instead of a tuyere.

12.9.4 Top Lances


A lance, while not required, greatly improves converter processes. In the high carbon region, a lance
can increase the oxygen input rate, increasing the decarburization rate. A lance can be used for postcombustion of carbon monoxide, increasing the scrap melting rate or temperature of the bath. For
small vessels, post-combustion lowers fueling requirements and increases process efficiency.
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Steelmaking and Refining Volume

The amount of oxygen that reacts with the bath can range from 30 to 100% of the oxygen blown.
This amount depends on lance height, nozzle design and gas pressure used.
There are two basic lance types, sonic/subsonic and supersonic. Sonic/subsonic lances consist of
straight pipes, while supersonic lances use converging/diverging (Laval) nozzles. Supersonic
lances are always water cooled. Sonic/subsonic lances might be water cooled depending on lance
operating position. Smaller sonic/subsonic lances often are not water cooled. Many sonic/subsonic
lances are simple pipes with nickel or calorized tips to increase heat resistance.
A water-cooled lance is typically positioned one to four metres from the bath surface. Non-watercooled lances are positioned close to the vessel mouth.
Supersonic lances are used for high oxygen input rates where post-combustion is not required. A
great majority of the oxygen from a supersonic lance will react with the bath.54 As in BOF operation, the lance can have post-combustion ports.
With sonic lances, some of the oxygen will not react with the bath; some post-combustion is
inevitable.55 Heat balances indicate that 75 to 90% of available energy from post-combustion is
transferred to the molten bath. The simplicity of a non-water-cooled sonic lance makes it attractive
to smaller shops.
Inert gases are sometimes injected with the oxygen from the top lance to extend the period the topblown gases are used. Argon top blowing can reduce air infiltration into the vessel and improve carbon removal efficiency in the late stages of the decarburization blow. This is especially true for vessels
where high rate bottom argon blowing causes excessive splashing, vibration, or refractory wear.
A recent development in top lance technology is the development of top heating. An oxy-fuel
burner in the top of the vessel provides heat to the vessel during operation.56 This results in benefits similar to post-combustion.

12.9.5 Gases
Pure argon, oxygen, and nitrogen are used by virtually all shops. In rare cases, nitrogen is not used
because the product mix or operation pattern does not warrant the extra cost of supplying nitrogen.
Some other gases used are crude argon, high-pressure air, non-cryogenic nitrogen and oxygen,
hydrocarbons, and carbon dioxide. These other gas choices depend on operational pattern, relative
cost of supply and product mix.
Crude argon contains 9597% argon, 13% oxygen, and 0.52% nitrogen. It can be used in the
middle to late stages of decarburization and reduction, depending on final product specifications.
The choice of using crude argon is dependent on availability, relative cost to pure argon, and product specifications.
High-pressure air can be used to partially replace nitrogen, but the capital and maintenance cost of
compressors and associated equipment limit this option to larger melt shops. Non-cryogenic nitrogen and oxygen sources also require some compression for use in refining processes, and the
choice of this supply method again depends on pure versus non-cryogenic prices, duty cycle, power
costs and production rates compared to pure gases.57
Carbon dioxide and hydrocarbons can be used as process gases down to certain carbon levels. In
stainless production, increased chromium oxidation below 0.3%C by carbon dioxide58 or hydrogen
and carbon pickup from hydrocarbons limits the use of these gases. The replacement of nitrogen
by these gases depends on the relative cost of the gases. Low nitrogen specification grades of stainless steel, which typically are made using only argon as an inert gas, can use carbon dioxide as a
replacement for argon in the early stages of decarburization.

12.9.6 Vessel Drive System


The drive system is similar to a BOF converter except that in most cases the vessel is removable
from the trunnion. Torque requirements and safety interlocks are an important design criteria.
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Some vessels are designed to rotate 360. Side-blown vessels generally have replaceable shells.
With removable vessels, crane access and capacity are considerations in the placement and size of
the operating unit.
The trunnion bearings and drive must be designed to handle the vibration and rocking motion of
the converter during processing.

12.9.7 Emissions Collection


Emissions collection strategies fall into two categories. Close capture hoods have a small gap, typically 0.2 to 0.4 metres, between the hood and vessel mouth. They are usually water cooled because
the hot gases cannot entrain enough dilution air to cool the gas. Alloy addition chutes and lance
positioning for alloy additions must be integrated with the hood. Other types of capture hoods are
further from the vessel mouth. These are usually refractory lined and not water cooled.
Canopy systems have a substantial distance from the vessel mouth to the collection duct that is
located in the roof of the shop. An accelerator stack is sometimes used as a chimney to direct the
smoke plume to the collection duct.
Baghouse fan capacity, crane location, emissions regulations and cost dictate the choice of emission collection system. Several systems use wet or dry precipitators in place of bags for dust collection. Top lance placement can hamper optimal placement of the collection hood. The lance will
have to penetrate the collection hood at some point. Close capture systems require less baghouse
capacity and are likely to emit less smoke, but water cooling duct work can be expensive.
Canopy systems will not operate effectively if the crane must pass through the plume periodically.
Baghouse requirements are usually higher because the baghouse must also take in dilution air that is
entrained into the rising smoke plume. On the plus side, water cooling of the canopy is usually not
necessary. However, placement of a lance with an accelerator stack system can be problematical.
The gas evolved from the converter is primarily CO along with argon or nitrogen, unless substantial post-combustion occurs. A major portion of the combustion and cooling takes place at the
mouth exit and/or at the hood intake. Further cooling takes place in the duct. By the time the gas
reaches the baghouse, the gas temperature is typically 120C. The gas is composed primarily of
CO2 and inert gas. Solids emissions from the converter are primarily particulates of metallic (e.g.,
iron, chromium and manganese) and non-metallic oxides (e.g., lime and silica). Total solids emissions average between 6 to 10 kg/ton of metal. Dust loading is about 50 grams/cubic metre. In the
United States, baghouse dust is normally handled by commercial processors.
For a new installation, the total cost of the fume system is typically about 40% of the total converter installation cost. In vacuum processes, the fume collection system is an integral part of the
equipment and typically is used in conjunction with a water treatment plant.

12.10 Vessel Operation


No matter what converter-based process is used for refining stainless steel, there are several common steps during the refining process. Decarburization is the carbon removal step. As decarburization is not completely efficient, some metallic oxides are formed. Reduction recovers these
oxides from the slag phase. Refining of the metal occurs throughout processing. Each of these
steps will be described in more detail.

12.10.1 Decarburization
After the molten charge is in the vessel, an oxygen-inert gas (argon, nitrogen, or carbon dioxide)
mixture is injected into the vessel. The initial oxygen to inert ratio generally varies in the range
of 5:1 to 3:1 and is lowered with the progress of decarburization. The major benefit associated
with the dilution process comes into play when the oxygen to inert gas ratio is 1:1 and then furCopyright 1998, The AISE Steel Foundation, Pittsburgh, PA. All rights reserved.

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Steelmaking and Refining Volume

ther reduced to 1:3 or lower. Oxidation of carbon continues, but oxidation of chromium is limited.
The latter is due to the very low oxygen potential of the gas mixture, which minimizes chromium
oxidation.
For a 300 series stainless, a typical stepped blow would be 1.5 Nm3/min/ton oxygen mixed with
0.5 Nm3/min/ton inert gas from the start carbon content to 0.35%C, then 0.5 Nm3/min/ton oxygen
mixed with 0.5 Nm3/min/ton inert gas to 0.15%C, followed by 0.25 Nm3/min/ton oxygen mixed
with 0.75 Nm3/min/ton inert gas to 0.05%C; and then 100% argon to final specification.
More recent blow programs consist of using a starting oxygen to inert gas ratio of higher than 3:1
and continuous adjustment of the oxygen to inert gas ratio during the blowing period. Depending
on the aim nitrogen content, nitrogen can be used as the inert gas for a period of the oxygen blow.
Beginning carbon levels in converter processing may range from 0.74.5%C, with a typical range
of 1.02.5%. Typical silicon levels range 0.20.4% before decarburization.
If a top lance is available, it is used during the high oxygen to inert gas periods. Some vessels use
a top lance to add heat. The top heating lance is a modified oxy-fuel burner.
During decarburization, additions are made for obtaining the proper final chemical composition.
These additions usually consist of desired amounts of high carbon ferrochromium, stainless steel
scrap, carbon steel scrap, nickel, iron, high carbon ferromanganese, and molybdenum oxide. These
additions serve to reduce the bath temperature as carbon and chromium oxidation are exothermic.
In general, the bath temperature is controlled to less than 1720C. Total alloy addition weights are
in the range of 530% of tap weight.
Lime or dolomitic limes are usually added just before the oxygen blow to flux the transfer slag and
silicon in the metal. During the oxygen blow, silicon is oxidized before carbon. Lime and dolomitic
lime are sometimes added before the end of the blow to cool the bath and to reduce the volume of
reduction additions. Slag fluxing additions, such as lime, dolomitic lime and spar, are typically in
the range of 37% total bath weight.
It follows that the length of the blow period is determined by the starting carbon and silicon levels
of the hot metal charged to the AOD. Decarburization times range from 20 to 35 minutes in modern converters (start carbon 1.5 to 2.5% and aim carbon 0.04%). Usually, the vessel is turned down
to a horizontal position and a sample of the melt is taken for analyses at a carbon level of about
0.1%. Some high productivity shops can sample without rotating the vessel by using a sub-lance.
The steel sample is analyzed for carbon. The temperature of the steel bath is also measured.
The next step is the reduction step, in which the reduction additions are charged and stirred with
an inert gas for a desired time. The reduction mix consists of silicon alloys, such as ferrosilicon or
chromium-silicon, and/or aluminum, which are added for the reduction of metallic oxides from the
slag and fluxing agents such as limestone, lime, dolomitic lime, and fluorspar. The bath is then
stirred with inert gas, typically for only for five to eight minutes. An example of a reduction mix
is given in Chapter 2, Section 2.9.3.
The formation of a high basicity slag and the reduction of oxygen potential in the metal bath are
good conditions for sulfur removal. For example, with a start sulfur of 0.03%, a reduction treatment of 23 kg aluminum/ton, 23 kg spar/ton, final slag basicity of about 1.7, and temperature of
1700C, finish sulfur contents of 0.0030.005% can be obtained.
If the grade to be produced requires an extra low sulfur level, the bath is deslagged after the reduction step and another basic slag is added. The liquid steel and the fluxes are then mixed to complete the desulfurization reaction. In modern practices a sulfur level of 0.001% or less is easily
achieved with this double slag practice.
Ideally, at this stage of the process, the chemistry of the liquid steel should meet final specifications so that the heat can be tapped. If necessary, additional raw materials may need to be charged
for small chemistry adjustments. Depending on the grade, additional deoxidation or alloying additions maybe needed. Such final additions are stirred in the AOD just before tap or are added in
the tap ladle.
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Refining of Stainless Steels

Following tap, the ladle is often stirred for composition homogenization and temperature uniformity along with flotation of inclusions. This is done in a ladle equipped with stirring facilities with
or without the use of a ladle furnace. After the ladle treatment, the steel is ready to be cast.

12.10.2 Refining
The amount of stirring energy from the gas blown through the subsurface tuyeres and the formation of carbon monoxide deep within the metal bath results in the converter processes being among
the most intensely stirred metallurgical reactors. The intimate gasmetal contact and excellent
slagmetal mixing facilitate refining reactions.
Sulfur removal is a slagmetal reaction that occurs during the reduction phase of the process.
Phosphorus, which requires oxidizing conditions, cannot be removed in the converter processing.
Nitrogen control is a gasmetal reaction. Depending on final nitrogen specifications for the stainless grade, the inert gas during the initial stages of decarburization can be nitrogen. After a certain
carbon level is achieved, the nitrogen gas is replaced by argon. Such an approach is practiced by
all steelmakers to reduce argon usage and costs and still achieve a desired nitrogen specification.
After the change from nitrogen to argon, nitrogen is removed from the bath by both evolved carbon monoxide and argon.59,60 Volatile elements with high vapor pressures, such as lead, zinc, and
bismuth, are removed during the decarburization period.61

12.10.3 Process Control


The nature and number of reactions makes mathematical modeling and process control of stainless
steel refining more complicated than standard pneumatic steelmaking.
Static calculation (i.e. no feedback) methods were used in the early days of stainless processing.
These calculations were standardized on worksheets that allowed operators to estimate temperature
changes, oxygen to inert gas ratio changes and nitrogen to argon changes. Reduction materials calculations were also performed.
With the introduction of powerful and inexpensive computers, dynamic calculations with automated
or manual correction can be employed. These allow the incorporation of sophisticated models for
temperature, blow program, nitrogen, and alloy addition control. Coupled with automated additions
systems, process variability has been much reduced and process efficiency has steadily improved.
Process control computer models (static, dynamic or hybrid) may utilize artificial intelligence to
control endpoint carbon and temperature levels and may eventually eliminate the need for sublances and/or offgas analyses. At a minimum, these programs advise the operator of blowing procedures, alloy and flux addition requirements and nitrogen switch-points, as well as provide data
logging. Many operators integrate the process control computer model with the gas control system
(valve rack) and some with other vessel functions (vessel rotation, additions, and fume system interfaces, sampling, etc.). These programs can be integrated with automated sampling equipment and/or
equipment for offgas analyses. The degree of control and process algorithm sophistication varies.

12.10.4 Post-Vessel Treatments


Post-converter vessel treatments after converter processing are similar to treatments for other steel
grades. Post-treatment facilities have several benefits: reduced converter tap-to-tap time, improved
quality, and an inventory buffer of metal between the converter and the continuous caster. The use
of ladle metallurgy furnaces for post-vessel treatments is increasing, especially in shops with continuous casting facilities.
Ladle treatment stations normally include an automated additions system, an injection lance or
porous plug for stirring with inert gas, and wire feeding equipment. Some producers use lances
to inject lime, fluorspar, and calcium alloys for quality improvements such as reduced inclusion
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737

Steelmaking and Refining Volume

content, inclusion shape control, improved weldability, and decreased dissolved oxygen levels.
Ladle additions of deoxidizing compounds are common. Wire feeding is used to add alloys of titanium, aluminum, calcium, and sulfur to improve alloy recoveries and quality.
Some operators use ladle furnaces to provide additional heat to perform the above operations.
Carbon pickup from the electrode arcs can be minimized by close control of slag thickness, arc
length and stirring rates, even when treating ultra-low carbon grades.
Shops having vacuum refining units would normally use these for the last stage of decarburization
on ultra-low carbon (ULC) and ultra-low nitrogen (ULN) grades or as part of the triplex (EAFConverter-VOD) process.

12.11 Summary
Stainless steels were developed at the beginning of the 20th century. Their unique properties have
led to their use in many different applications. Fundamental research in the thermodynamics and
kinetics led to understanding of the phenomenon associated with chromium oxidation and how to
minimize it. The development of the argon oxygen decarburization (AOD) process revolutionized
stainless steelmaking. This process, based on the dilution principle, allowed steelmakers to use
lower cost raw materials and to shorten the steelmaking times compared to the other processes in
use at that time. This led to lowering the cost of producing stainless steels. This, in turn, led to dramatic increases in the applications for stainless steels. Over the years, other processes have been
developed for making stainless steels. Most of these use vessels or reactors in which gases are
introduced to carry out the necessary decarburization reactions. Some of these processes for making stainless steels utilize decarburization under vacuum.
Of the many specific processes available for stainless steel refining, argon oxygen decarburization
and its converter-based variants are by far the most commercially popular. For maximum flexibility to produce a very wide range of stainless steel grades, a modern melt shop may have a source
of molten metal, a converter that can produce most grades economically (duplex processing) and
a vacuum unit for further processing of extra low carbon and nitrogen grades (triplex processing).

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